本揭露提供聚碳酸酯及其製法,該聚碳酸酯具有好耐候性與折射率,同時具有極佳機械性質。
本揭露提供聚碳酸酯,其包括化學式1表示之重複單元。
另外,本揭露提供聚碳酸酯的製法,其包括將含有化學式3表示之化合物、與碳酸酯前驅物的組成物聚合之步驟。
此外,本揭露提供使用聚碳酸酯製成之模製物件。
在下文,將根據本揭露的特定示範性實施方式更詳細說明聚碳酸酯、其製法、與模製物件。
[發明之詳細說明]
根據本揭露的一個示範性實施方式,提供聚碳酸酯,其包括下列化學式1表示之重複單元:
[化學式1]
在化學式1中,
X是未經取代或經C1-10
烷基取代之C6-60
伸芳基,
Y是氧(O)、或硫(S),及
n為1至10的整數。
聚碳酸酯具有包括鍵聯在5員雜環基周圍的各種伸芳基之官能基的新穎結構,並且可另外展現好耐候性、折射率特性等,且同時具有為現存聚碳酸酯中固有的特性之極佳耐衝擊性、透明度、耐熱性等。
更特別地,化學式1之重複單元(其形成本揭露的聚碳酸酯)包括具有彼此鍵聯之酯基與5員雜環基的結構,可由於酯基之Fries重排反應所導致的結構改變而展現比現存聚碳酸酯更佳之耐候性與折射率效果,及可視在化學式1的結構和取代基X與Y之各種結構中所包括的重複單元之含量(n)而定另外增加改善聚碳酸酯的耐候性與折射率之效果。
本揭露之聚碳酸酯可僅具有化學式1表示之重複單元。或者,這樣的聚碳酸酯除了化學式1表示之重複單元之外,還可另外包括由其他芳族二醇化合物衍生之重複單元。
根據一個示範性實施方式,本揭露之聚碳酸酯可包括化學式1表示之重複單元與下列化學式2重複著的重複單元:
[化學式2]
在化學式2中,
R1
至R4
各獨立地為氫、C1-10
烷基、C1-10
烷氧基、或鹵素,及
Z是未經取代或經苯基取代之C1-10
伸烷基、未經取代或經C1-10
烷基取代的C3-15
伸環烷基、O、S、SO、SO2
、或CO。
在本說明書中,具有6至60個碳原子之伸芳基可為單環伸芳基或多環伸芳基。特別地,具有6至60個碳原子之伸芳基可為具有6至30個碳原子的單環或多環之伸芳基;或具有6至20個碳原子之單環或多環的伸芳基。更特別地,具有6至60個碳原子之伸芳基對於單環伸芳基可為由例如苯、聯苯、二苯甲烷、二苯丙烷、聯三苯等的芳族烴衍生的二價基團,對於多環芳基可為由例如萘、蒽、菲、聯伸三苯、芘、苝、䓛、茀等的芳族烴衍生之二價基團,但不限於此。另外,具有6至60個碳原子之伸芳基可為未經取代或經具有1至10個碳原子的烷基取代。
在本說明書中,茀可經取代,或可以二個取代基彼此結合的方式形成螺結構。當茀經取代時,茀可為等,但不限於此。
在本說明書中,烷基可為具有1至10個碳原子,或1至5個碳原子的直鏈或支鏈烷基。作為烷基之具體實例,有甲基、乙基、丙基、正丙基、異丙基、丁基、正丁基、異丁基、三級丁基、二級丁基、1-甲基-丁基、1-乙基-丁基、戊基、正戊基、異戊基、新戊基、三級戊基、己基、正己基、1-甲基戊基、2-甲基戊基、4-甲基-2-戊基、3,3-二甲基丁基、2-乙基丁基、庚基、正庚基、1-甲基己基、辛基、正辛基、三級辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、正壬基、2,2-二甲基庚基、1-乙基-丙基、1,1-二甲基-丙基、異己基、2-甲基戊基、4-甲基己基、5-甲基己基等,但不限於此。
根據本揭露之一個實施方式,在化學式1中,Y是氧(O)或硫(S)。
另外,在化學式1中,X可為,,或。
此外,在化學式1中,n為1至10、1至8、或1至4的整數。
此外,在化學式2中,R1
至R4
各獨立地為氫、或C1-4
烷基。較佳地,R1
至R4
可各獨立地為氫、甲基、氯、或溴。
另外,在化學式2中,Z各獨立地為未經取代或經苯基取代之直鏈或支鏈C1-10
伸烷基,且更佳地可為伸甲基、乙烷-1,1-二基、丙烷-2,2-二基、丁烷-2,2-二基、1-苯基乙烷-1,1-二基、或二苯伸甲基。
化學式1表示之重複單元的特徵在於極佳折射率、流動性與耐候性,同時化學式2表示之重複單元的特徵在於極佳透明度與耐衝擊性。因此,可調整化學式1與2表示之重複單元的重量比以製備具有所欲物理性質之聚碳酸酯。
當本揭露之聚碳酸酯除了化學式1表示的重複單元之外另外包括化學式2表示的重複單元時,其重量比未特別限制。例如,化學式1表示之重複單元與化學式2表示之重複單元的重量比可為99:1至1:99。
例如,對高折射率而言,這樣的聚碳酸酯可包括以重複單元總重量為基準計多於50重量%、60重量%或更多、或70重量%或更多,且99重量%或更少,較佳為多於50重量%且99重量%或更少,且更佳為70至99重量%的化學式1表示之重複單元。同時,對高折射率而言,本揭露之聚碳酸酯可僅由化學式1表示之重複單元形成,亦即以重複單元總重量為基準計100重量%的化學式1表示之重複單元。
另一方面,對改善耐候性的效果而言,這樣的聚碳酸酯可包括以重複單元總重量為基準計5重量%或更多、或10重量%或更多,且50重量%或更少,較佳為5至30重量%,且更佳為10至30重量%的化學式1表示之重複單元。
另外,如果化學式1中Y是硫,這情況可顯示更有利於高折射率之特性。如果Y是氧,這情況可展現更有利於耐候性的特性。
此外,即使取決於化學式1中X的結構,亦可展現各種特性。如果X是以茀為基礎之結構,則可更佳地實現高折射率特性。
如上所示,利用適當地調整在整個聚碳酸酯中取代基X與Y之類型與其含量的方式,可提供具有適合於其目的之所欲物理性質的新穎聚碳酸酯。
聚碳酸酯的重量平均分子量(Mw)可依據其目的與用途而適當地調整,且重量平均分子量可為28,000 g/mol或更多、37,000 g/mol或更多、或38,000 g/mol或更多,且60,000 g/mol或更少、55,000 g/mol或更少、或52,000 g/mol或更少,此係利用凝膠滲透層析法(GPC)測量並使用標準聚苯乙烯(PS標準物)校準。
另外,根據ASTM D1238 (300℃,1.2 kg條件)測得之聚碳酸酯的熔融指數可依據其目的與用途而適當地調整,並且可為3 g/10分鐘或更多、5 g/10分鐘或更多、或7 g/10分鐘或更多,且30 g/10分鐘或更少、20 g/10分鐘或更少、或15 g/10分鐘或更少。
此外,根據JIS-K-7142測得之本揭露的聚碳酸酯之折射率(nD)可為1.58或更多,較佳為1.58至1.68、或1.59至1.67,且更佳為1.60至1.67。
此外,利用根據ASTM D7869,測量樣本之L、a與b值及將該樣本留在風化條件中2250 hr後用Weather-Ometer®機器再度測量L'、a'與b'值方式,計算出的本揭露之聚碳酸酯的耐候性指數(ΔE)可為31或更少,且較佳為30或更少、29或更少、25或更少、20或更少、15或更少、13或更少、或11或更少。較低的耐候性可以被評估為較佳。從而,其下限未特別限制,但可為例如1或更多、3或更多、5或更多、7或更多、或8或更多。
同時,根據本揭露之另一個示範性實施方式,可提供聚碳酸酯的製法,其包括將含有下列化學式3表示之化合物、與碳酸酯前驅物的組成物聚合之步驟:
[化學式3]
在化學式3中,
X是未經取代或經C1-10
烷基取代之C6-60
伸芳基,
Y是氧(O)、或硫(S),及
n為1至10的整數。
根據本揭露之一個實施方式,在化學式3中,n可為1或更多、2或更多、或3或更多,且10或更少、8或更少、6或更少、或4或更少的整數。
另外,在組成物中,可含有n分別為1至10範圍內的化學式3之化合物的混合物。
根據本揭露之一個實施方式,化學式3之化合物的重量平均分子量可依據其目的與用途而適當地調整,且該重量平均分子量可為300 g/mol或更多、500 g/mol或更多、或700 g/mol或更多,且5,000 g/mol或更少、3,500 g/mol或更少、或2,000 g/mol或更少,其係利用凝膠滲透層析法(GPC)測量並使用標準聚苯乙烯(PS標準物)校準。
根據本揭露之一個實施方式,在化學式3中,Y是氧(O)或硫(S)。
另外,在化學式3中,X可為,,或。
此外,在化學式3中,n為1至10、1至8、或1至4的整數。化學式3表示之化合物可單獨或以一或多種混合形式被使用。
作為化學式3表示之化合物的具體實例,可有下列結構式之化合物,但本揭露不限於此:與
在上述結構式中,n係如化學式3中所定義。
化學式3表示之化合物可藉由根據下列反應式1的酯化反應來合成,且更具體的細節將在後述實施方式中提到:
[反應式1]
在上述反應式1中,X、Y與n係如化學式3中所定義。
根據本揭露之一個實施方式,此化合物可經由另外含有下列化學式4表示之芳族二醇化合物而聚合:
[化學式4]
在化學式4中,
R1
至R4
各獨立地為氫、C1-10
烷基、C1-10
烷氧基、或鹵素,及
Z是未經取代或經苯基取代之C1-10
伸烷基、未經取代或經C1-10
烷基取代的C3-15
伸環烷基、O、S、SO、SO2
、或CO。
作為化學式4表示之芳族二醇化合物的具體實例,可包括選自由下列所組成之群組的至少一種化合物:雙(4-羥基苯基)甲烷、雙(4-羥基苯基)醚、雙(4-羥基苯基)碸、雙(4-羥基苯基)亞碸、雙(4-羥基苯基)硫醚、雙(4-羥基苯基)酮、1,1-雙(4-羥基苯基)乙烷、2,2-雙(4-羥基苯基)丙烷(雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷(雙酚Z)、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-溴苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、及1,1-雙(4-羥基苯基)-1-苯基乙烷。
另外,碳酸酯前驅物可以使化學式3表示之化合物與化學式4表示之化合物彼此鍵聯。作為其具體實例,可有光氣、三光氣、雙光氣、溴光氣、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯、碳酸二環己酯、碳酸二苯酯、碳酸二甲苯酯、碳酸雙(氯苯基)酯、碳酸間甲苯酯、碳酸二萘酯、碳酸雙(二苯基)酯或雙鹵甲酸酯。
如果組成物僅含有化學式3表示之化合物與碳酸酯前驅物作為單體,可使用以100重量%的組成物為基準計,70重量%或更多、79重量%或更多、或80重量%或更多,且95重量%或更少、90重量%或更少、或89%或更少的化學式3表示之化合物。
另外,可使用以100重量%的組成物為基準計,10重量%或更多、19重量%或更多、或20重量%或更多,且35重量%或更少、30重量%或更少、或29%或更少的碳酸酯前驅物。
同時,在聚合反應期間,如果組成物含有化學式3表示之化合物、化學式4表示之芳族二醇化合物、與碳酸酯前驅物作為單體,可使用以100重量%的組成物為基準計,10重量%或更多、20重量%或更多、或30重量%或更多,且70重量%或更少、50重量%或更少、或40%或更少的化學式3表示之化合物。
另外,可使用以100重量%的組成物為基準計,10重量%或更多、20重量%或更多、或30重量%或更多,且70重量%或更少、50重量%或更少、或40%或更少的化學式4表示之芳族二醇化合物。
此外,可使用以100重量%的組成物為基準計,10重量%或更多、19重量%或更多、或20重量%或更多,且35重量%或更少、30重量%或更少、或29%或更少的碳酸酯前驅物。
此時,較佳為進行界面聚合反應形式的聚合反應。在界面聚合反應期間,聚合反應是可行的,並且可在常壓與低溫下容易地調整分子量。
較佳為聚合反應溫度是0℃至40℃,且反應時間是10分鐘至5小時。另外,較佳為在反應期間將pH保持於9或更多、或11或更多。
任何溶劑均可用於聚合反應而無特別限制,只要在該領域中該溶劑被用於聚碳酸酯之聚合反應即可。例如,可使用鹵化烴類例如二氯甲烷、氯苯等。
另外,較佳為聚合反應係在酸黏合劑存在下進行。作為酸黏合劑,可使用下列:鹼金屬氫氧化物(例如氫氧化鈉、氫氧化鉀等),或胺化合物(例如吡啶等)。
此外,較佳為聚合反應係在分子量調節劑存在下進行,以便在聚合反應期間控制聚碳酸酯之分子量。作為分子量調節劑,可使用C1-20
烷基酚。作為其具體實例,可有對三級丁基酚、對茴香基酚、癸基酚、十二基酚、十四基酚、十六基酚、十八基酚、二十基酚、二十二基酚或三十基酚。在聚合反應開始之前、期間與之後可加入分子量調節劑。每100重量份的芳族二醇化合物可使用0.01至10重量份,較佳為0.1至6重量份之量的分子量調節劑,並且可獲得在該範圍內之所欲分子量。
另外,可另外使用反應加速劑(例如三級胺化合物、四級銨化合物、四級鏻化合物等),例如三乙胺、溴化四正丁銨、溴化四正丁鏻等,以便加速聚合反應。
根據本揭露之另一個示範性實施方式,可提供使用聚碳酸酯製成的模製物件。如上所述,包括化學式1表示之重複單元的聚碳酸酯也具有耐候性改善,同時具有極佳機械性質,從而具有比使用現存聚碳酸酯製成之模製物件更廣的應用領域。可調整化學式1與2表示之重複單元的重量比,藉以製備具有所欲物理性質之聚碳酸酯。
除了根據本揭露之聚碳酸酯之外,模製物件還可含有選自由下列所組成之組群中的至少一者:抗氧化劑、塑化劑、抗靜電劑、成核劑、阻燃劑、潤滑劑、衝擊改性劑、螢光亮光劑、紫外線吸收劑、顏料及染料,如果必要。
作為模製物件之製法的一個實例,可包括下列步驟:用混合器充分混合本發明之聚碳酸酯與其他添加劑,然後用擠製機進行擠製成型以製造丸料,然後乾燥丸料,然後用射出成型機進行射出。
根據本揭露,可提供聚碳酸酯及其製法,該聚碳酸酯具有耐候性與折射率改善的新穎結構,同時具有極佳機械性質。The present disclosure provides polycarbonate and its preparation method. The polycarbonate has good weather resistance and refractive index, and has excellent mechanical properties at the same time. The present disclosure provides polycarbonate including the repeating unit represented by Chemical Formula 1. In addition, the present disclosure provides a method for producing polycarbonate, which includes the step of polymerizing a composition comprising a compound represented by Chemical Formula 3 and a carbonate precursor. Additionally, the present disclosure provides molded articles made using polycarbonate. Hereinafter, polycarbonate, its manufacturing method, and molded objects will be described in more detail according to certain exemplary embodiments of the present disclosure. [Detailed Description of the Invention] According to an exemplary embodiment of the present disclosure, there is provided a polycarbonate including a repeating unit represented by the following Chemical Formula 1: [Chemical Formula 1] ![Figure 02_image001](https://patentimages.storage.***apis.com/5a/7c/28/7967ca095fff80/02_image001.png)
In Chemical Formula 1, X is a C 6-60 arylylene group that is unsubstituted or substituted by a C 1-10 alkyl group, Y is oxygen (O) or sulfur (S), and n is an integer from 1 to 10. Polycarbonate has a novel structure including functional groups of various aryl groups bonded around a 5-membered heterocyclic group, and can additionally exhibit good weather resistance, refractive index characteristics, etc. Excellent impact resistance, transparency, heat resistance, etc. More specifically, the repeating unit of Chemical Formula 1 (which forms the polycarbonate of the present disclosure) includes a structure having an ester group and a 5-membered heterocyclic group linked to each other, which may be changed due to a Fries rearrangement reaction of the ester group And exhibit better weather resistance and refractive index effect than the existing polycarbonate, and can increase the content (n) of repeating units included in the structure of chemical formula 1 and the various structures of the substituents X and Y to increase and improve the polycarbonate Effect of weather resistance and refractive index of ester. The polycarbonate of the present disclosure may only have the repeating unit represented by Chemical Formula 1. Alternatively, such a polycarbonate may further include repeating units derived from other aromatic diol compounds in addition to the repeating units represented by Chemical Formula 1. According to an exemplary embodiment, the polycarbonate of the present disclosure may include a repeating unit represented by Chemical Formula 1 and a repeating unit of the following Chemical Formula 2: [Chemical Formula 2] In Chemical Formula 2, R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1-10 alkoxy, or halogen, and Z is unsubstituted or phenyl-substituted C 1-10 alkylene, unsubstituted or C 1-10 alkyl substituted C 3-15 cycloalkylene, O, S, SO, SO 2 , or CO. In the present specification, the arylylene group having 6 to 60 carbon atoms may be a monocyclic arylylene group or a polycyclic arylylene group. In particular, the arylylene group having 6 to 60 carbon atoms may be a monocyclic or polycyclic arylylene group having 6 to 30 carbon atoms; or a monocyclic or polycyclic arylylene group having 6 to 20 carbon atoms. Aryl. More particularly, the arylylene group having 6 to 60 carbon atoms may be a divalent one derived from an aromatic hydrocarbon such as benzene, biphenyl, diphenylmethane, diphenylpropane, terphenyl, etc. for a monocyclic arylylene group. The group, for the polycyclic aryl group, may be a divalent group derived from an aromatic hydrocarbon such as naphthalene, anthracene, phenanthrene, triphenylene, pyrene, perylene, perylene, perylene, etc., but is not limited thereto. In addition, the arylylene group having 6 to 60 carbon atoms may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. In this specification, tertiles may be substituted, or two substituents may be combined to form a spiro structure. When fennel is substituted, fennel can be etc., but not limited to this. In the present specification, the alkyl group may be a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, 1-methyl -Butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl , 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tertiary Octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-di Methyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but not limited thereto. According to an embodiment of the present disclosure, in Chemical Formula 1, Y is oxygen (O) or sulfur (S). In addition, in Chemical Formula 1, X can be , ,or . Also, in Chemical Formula 1, n is an integer of 1 to 10, 1 to 8, or 1 to 4. In addition, in Chemical Formula 2, R 1 to R 4 are each independently hydrogen or C 1-4 alkyl. Preferably, R 1 to R 4 can each independently be hydrogen, methyl, chlorine, or bromine. In addition, in Chemical Formula 2, Z is each independently unsubstituted or phenyl-substituted straight or branched C 1-10 alkylene, and more preferably can be methylene, ethane-1,1 -diyl, propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or dibenzylidene. The repeating unit represented by Chemical Formula 1 is characterized by excellent refractive index, fluidity and weather resistance, while the repeating unit represented by Chemical Formula 2 is characterized by excellent transparency and impact resistance. Therefore, the weight ratio of the repeating units represented by Chemical Formulas 1 and 2 can be adjusted to prepare polycarbonate with desired physical properties. When the polycarbonate of the present disclosure further includes the repeating unit represented by Chemical Formula 1 in addition to the repeating unit represented by Chemical Formula 1, the weight ratio thereof is not particularly limited. For example, the weight ratio of the repeating unit represented by Chemical Formula 1 to the repeating unit represented by Chemical Formula 2 may be 99:1 to 1:99. For example, for a high refractive index, such polycarbonates may comprise greater than 50 wt%, 60 wt% or more, or 70 wt% or more, and 99 wt% or Less, preferably more than 50% by weight and 99% by weight or less, and more preferably 70 to 99% by weight of the repeating unit represented by Chemical Formula 1. Meanwhile, for high refractive index, the polycarbonate of the present disclosure may be formed only of the repeating unit represented by Chemical Formula 1, that is, 100% by weight of the repeating unit represented by Chemical Formula 1 based on the total weight of the repeating units. On the other hand, for the effect of improving weather resistance, such polycarbonate may contain 5% by weight or more, or 10% by weight or more, and 50% by weight or less, based on the total weight of repeating units. , preferably 5 to 30% by weight, and more preferably 10 to 30% by weight of the repeating unit represented by Chemical Formula 1. In addition, if Y in Chemical Formula 1 is sulfur, this situation may show more favorable characteristics of high refractive index. If Y is oxygen, this case can exhibit characteristics more favorable for weather resistance. In addition, even depending on the structure of X in Chemical Formula 1, various characteristics may be exhibited. If X is a fennel-based structure, high refractive index characteristics can be better realized. As shown above, by appropriately adjusting the type and content of the substituents X and Y in the overall polycarbonate, a novel polycarbonate having desired physical properties suitable for its purpose can be provided. The weight average molecular weight (Mw) of polycarbonate can be appropriately adjusted depending on its purpose and use, and the weight average molecular weight may be 28,000 g/mol or more, 37,000 g/mol or more, or 38,000 g/mol or more more than 60,000 g/mol or less, 55,000 g/mol or less, or 52,000 g/mol or less as measured by gel permeation chromatography (GPC) and using standard polystyrene (PS standard object) calibration. In addition, the melt index of polycarbonate measured according to ASTM D1238 (300°C, 1.2 kg condition) can be adjusted appropriately depending on its purpose and use, and can be 3 g/10 minutes or more, 5 g/10 minutes or more, or 7 g/10 minutes or more, and 30 g/10 minutes or less, 20 g/10 minutes or less, or 15 g/10 minutes or less. In addition, the polycarbonate of the present disclosure may have a refractive index (nD) of 1.58 or more, preferably 1.58 to 1.68, or 1.59 to 1.67, and more preferably 1.60 to 1.67, measured according to JIS-K-7142. In addition, by measuring the L, a and b values of the sample according to ASTM D7869 and leaving the sample in weathering conditions for 2250 hrs and then measuring the L', a' and b' values again with a Weather-Ometer® machine, the calculated The weather resistance index (ΔE) of the polycarbonate of the present disclosure can be 31 or less, and preferably 30 or less, 29 or less, 25 or less, 20 or less, 15 or less, 13 or less, or 11 or less. Lower weather resistance can be evaluated as better. Thus, the lower limit thereof is not particularly limited, but may be, for example, 1 or more, 3 or more, 5 or more, 7 or more, or 8 or more. At the same time, according to another exemplary embodiment of the present disclosure, a method for producing polycarbonate can be provided, which includes the step of polymerizing a composition containing a compound represented by the following chemical formula 3 and a carbonate precursor: [chemical formula 3] In Chemical Formula 3, X is an unsubstituted or C 1-10 alkyl substituted C 6-60 arylylene group, Y is oxygen (O) or sulfur (S), and n is an integer from 1 to 10. According to an embodiment of the present disclosure, in Chemical Formula 3, n may be 1 or more, 2 or more, or 3 or more, and 10 or less, 8 or less, 6 or less, or 4 or less integers. In addition, in the composition, a mixture of compounds of Chemical Formula 3 in which n is in the range of 1 to 10, respectively, may be contained. According to one embodiment of the present disclosure, the weight average molecular weight of the compound of chemical formula 3 can be appropriately adjusted according to its purpose and use, and the weight average molecular weight can be 300 g/mol or more, 500 g/mol or more, or 700 g/mol or more, and 5,000 g/mol or less, 3,500 g/mol or less, or 2,000 g/mol or less, which are measured by gel permeation chromatography (GPC) and used Standard polystyrene (PS standard) calibration. According to an embodiment of the present disclosure, in Chemical Formula 3, Y is oxygen (O) or sulfur (S). In addition, in Chemical Formula 3, X can be , ,or . Also, in Chemical Formula 3, n is an integer of 1 to 10, 1 to 8, or 1 to 4. The compounds represented by Chemical Formula 3 may be used alone or in admixture of one or more. As a specific example of the compound represented by Chemical Formula 3, there may be a compound of the following structural formula, but the present disclosure is not limited thereto: and In the above structural formula, n is as defined in Chemical Formula 3. The compound represented by chemical formula 3 can be synthesized by the esterification reaction according to the following reaction formula 1, and more specific details will be mentioned in the following embodiments: [reaction formula 1] In the above Reaction Formula 1, X, Y and n are as defined in Chemical Formula 3. According to one embodiment of the present disclosure, this compound can be polymerized by additionally containing an aromatic diol compound represented by the following chemical formula 4: [chemical formula 4] In Chemical Formula 4, R 1 to R 4 are each independently hydrogen, C 1-10 alkyl, C 1-10 alkoxy, or halogen, and Z is unsubstituted or phenyl-substituted C 1-10 alkylene, unsubstituted or C 1-10 alkyl substituted C 3-15 cycloalkylene, O, S, SO, SO 2 , or CO. Specific examples of the aromatic diol compound represented by Chemical Formula 4 may include at least one compound selected from the group consisting of bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) phenylene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxy Phenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl) base) cyclohexane (bisphenol Z), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl) ) propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3 -Methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane . In addition, the carbonate precursor may link the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 to each other. As specific examples thereof, there may be phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, xylene carbonate ester, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate or bishaloformate. If the composition contains only the compound represented by Chemical Formula 3 and the carbonate precursor as monomers, 70% by weight or more, 79% by weight or more, or 80% by weight can be used based on 100% by weight of the composition. or more, and 95% by weight or less, 90% by weight or less, or 89% or less of the compound represented by Chemical Formula 3. In addition, based on 100% by weight of the composition, 10% by weight or more, 19% by weight or more, or 20% by weight or more, and 35% by weight or less, 30% by weight or more less, or 29% or less carbonate precursor. At the same time, during the polymerization reaction, if the composition contains the compound represented by Chemical Formula 3, the aromatic diol compound represented by Chemical Formula 4, and the carbonate precursor as monomers, based on 100% by weight of the composition, 10 % by weight or more, 20% by weight or more, or 30% by weight or more, and 70% by weight or less, 50% by weight or less, or 40% or less of the compound represented by Chemical Formula 3. In addition, based on 100% by weight of the composition, 10% by weight or more, 20% by weight or more, or 30% by weight or more, and 70% by weight or less, 50% by weight or more Less, or 40% or less, of the aromatic diol compound represented by Chemical Formula 4. In addition, based on 100% by weight of the composition, 10% by weight or more, 19% by weight or more, or 20% by weight or more, and 35% by weight or less, 30% by weight or more less, or 29% or less carbonate precursor. At this time, it is preferable to conduct the polymerization in the form of interfacial polymerization. During interfacial polymerization, polymerization is feasible, and molecular weight can be easily adjusted at normal pressure and low temperature. Preferably, the polymerization reaction temperature is 0°C to 40°C, and the reaction time is 10 minutes to 5 hours. In addition, it is preferable to keep the pH at 9 or more, or 11 or more during the reaction. Any solvent may be used for the polymerization reaction without particular limitation as long as the solvent is used for the polymerization reaction of polycarbonate in this field. For example, halogenated hydrocarbons such as dichloromethane, chlorobenzene, and the like can be used. In addition, it is preferred that the polymerization reaction is carried out in the presence of an acid binder. As the acid binder, the following can be used: alkali metal hydroxides (such as sodium hydroxide, potassium hydroxide, etc.), or amine compounds (such as pyridine, etc.). In addition, it is preferred that the polymerization is carried out in the presence of a molecular weight regulator in order to control the molecular weight of the polycarbonate during the polymerization. As a molecular weight regulator, C 1-20 alkylphenols can be used. As specific examples thereof, p-tertiary butylphenol, p-anisylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, eicosylphenol, Diylphenol or triacylphenol. Molecular weight regulators can be added before, during and after the initiation of the polymerization. The molecular weight regulator may be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight, per 100 parts by weight of the aromatic diol compound, and a desired molecular weight within this range may be obtained. In addition, a reaction accelerator (such as a tertiary amine compound, a quaternary ammonium compound, a quaternary phosphonium compound, etc.), such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, etc., can be additionally used in order to accelerate the polymerization reaction. According to another exemplary embodiment of the present disclosure, a molded article made using polycarbonate may be provided. As described above, the polycarbonate including the repeating unit represented by Chemical Formula 1 also has improved weather resistance while having excellent mechanical properties, thereby having wider application fields than molded articles made using existing polycarbonates. The weight ratio of the repeating units represented by Chemical Formulas 1 and 2 can be adjusted to prepare polycarbonate with desired physical properties. In addition to the polycarbonate according to the present disclosure, the molded article may also contain at least one selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, Lubricants, impact modifiers, fluorescent brighteners, UV absorbers, pigments and dyes, if necessary. As an example of a method for molding a molded article, the following steps may be included: thoroughly mixing the polycarbonate of the present invention and other additives with a mixer, then extruding with an extruder to produce pellets, and then drying the pellets, Then it is injected with an injection molding machine. According to the present disclosure, polycarbonate and its preparation method can be provided. The polycarbonate has a novel structure with improved weather resistance and refractive index, and has excellent mechanical properties at the same time.
將透過下列實施方式更詳細說明本揭露。然而,提供下列實施方式只為了說明本揭露,從而本揭露不限於此。
[實施例] 聚碳酸酯之製備
實施例1
(1) BP-TPDCA (雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯)之製備
將15 g噻吩-2,5-二甲酸於圓底燒瓶中溶於100 ml二氯甲烷溶劑,隨後在室溫逐滴加入24.3 g乙二醯氯與0.29 g DMF,及在室溫攪拌約4小時。當所得之反應物變成透明且未形成任何泡沫時,在無個別純化程序下將反應物慢慢加到41.7 g雙酚A、27.6 g吡啶與200 ml二氯甲烷溶劑,及在室溫攪拌24小時。加入50 ml 35% HCl以終止反應,然後用水與二氯甲烷清洗。獲得最終產率92%的最終化合物,亦即雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯(重量平均分子量:1,300 g/mol)。此時,獲得混合物形式之化合物,其中n分別為1至4。
圖1顯示化合物之1
H-NMR (CDCl3
-d1
)。
(2) 聚碳酸酯樹脂之製備
將247 g水、上述(1)中所製得之138.8 g雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯、41 g 40重量% NaOH、與165 ml MeCl2
放入2 L主反應器中,該主反應器配備氮氣沖刷與冷凝器,且可用環流器保持於室溫,然後攪拌數分鐘。
在停止氮氣沖刷後,將23 g三光氣與60 g MeCl2
放入1 L圓底燒瓶中以溶解其中的三光氣,隨後將所得之經溶解的三光氣溶液慢慢放入主反應器中,其中BP-TPDCA溶液已經溶解。加完後,放入1 g PTBP (對三級丁基酚)且攪拌約10分鐘。攪動完後,放入39.8 g 40重量% NaOH水溶液,使得放入0.42 g TEA作為偶合劑。此時,將反應pH保持於11至13。將所得之混合物獨留一段時間以徹底地進行反應,隨後放入HCl以終止反應,使得pH降到3至4。然後,停止攪動,隨後將聚合物層與水層彼此分離,重複地進行三至五次移除水層並再次放入純H2
O的清洗程序。
當清洗徹底完成時,只萃取出聚合物層,隨後經由再沉澱法使用非溶劑(例如甲醇、H2
O等)以獲得聚合物晶體。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為50,000 g/mol。
實施例2
(1) BP-FDCA (雙(4-(2-(4-羥基苯基)丙-2-基)苯基)呋喃-2,5-二甲酸酯)之製備
以相同於實施例1之方式進行合成,但是用15 g 2,5-呋喃二甲酸替代實施例1的噻吩-2,5-二甲酸,及使用26.8 g乙二醯氯、0.33 g DMF、46.1 g雙酚A、與30.4 g吡啶。
獲得最終產率87%的最終化合物,亦即雙(4-(2-(4-羥基苯基)丙-2-基)苯基)呋喃-2,5-二甲酸酯(重量平均分子量:1,250 g/mol)。此時,獲得混合物形式之化合物,其中n分別為1至4。
圖2顯示化合物之1
H-NMR (丙酮-d6
)。
(2) 聚碳酸酯樹脂之製備
以相同於實施例1之聚碳酸酯樹脂的製法之方式製得聚碳酸酯,但是使用上述(1)中所製得之126.7 g雙(4-(2-(4-羥基苯基)丙-2-基)苯基)呋喃-2,5-二甲酸酯替代實施例1的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為50,000 g/mol。
實施例3
(1) BHP-TPDCA (雙(3-羥基苯基)噻吩-2,5-二甲酸酯)之製備
以相同於實施例1之方式進行合成,但是使用實施例1之15 g噻吩-2,5-二甲酸,及使用20.1 g間苯二酚與41.4 g吡啶替代24.3 g乙二醯氯、0.29 g DMF、與雙酚A。
獲得最終產率97%的最終化合物,亦即雙(3-羥基苯基)噻吩-2,5-二甲酸酯(重量平均分子量:850 g/mol)。此時,獲得混合物形式之化合物,其中n分別為1至4。
圖3顯示化合物之1
H-NMR (丙酮-d6
)。
(2) 聚碳酸酯樹脂之製備
以相同於實施例1之聚碳酸酯樹脂的製法之方式製得聚碳酸酯,但是使用上述(1)中所製得之75.4 g雙(3-羥基苯基)噻吩-2,5-二甲酸酯替代實施例1的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。
實施例4
(1) BPF-TPDCA (雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯)之製備
以相同於實施例1之方式進行合成,但是使用實施例1之15 g噻吩-2,5-二甲酸,及使用62.6 g 4,4'-(9H-茀-9,9-二基)二酚與41.4 g吡啶替代24.3 g乙二醯氯、0.29 g DMF、與雙酚A。
獲得最終產率81%的最終化合物,亦即雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯(重量平均分子量:1,800 g/mol)。此時,獲得混合物形式之化合物,其中n分別為1至4。
圖4顯示化合物之1
H-NMR (丙酮-d6
)。
(2) 聚碳酸酯樹脂之製備
以相同於實施例1之聚碳酸酯樹脂的製法之方式製得聚碳酸酯,但是使用上述(1)中所製得之195.9 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯替代實施例1的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為50,000 g/mol。
實施例5
(1) BPF-FDCA (雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)呋喃-2,5-二甲酸酯)之製備
以相同於實施例1之方式進行合成,但是使用15 g 2,5-呋喃二甲酸替代實施例1之噻吩-2,5-二甲酸,及使用69 g 4,4'-(9H-茀-9,9-二基)二酚與45.6 g吡啶替代26.8 g乙二醯氯、0.33 g DMF、與雙酚A。
獲得最終產率91%的最終化合物,亦即雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)呋喃-2,5-二甲酸酯(重量平均分子量:1,760 g/mol)。此時,獲得混合物形式之化合物,其中n分別為1至4。
圖5顯示化合物之1
H-NMR (丙酮-d6
)。
(2) 聚碳酸酯樹脂之製備
以相同於實施例1之聚碳酸酯樹脂的製法之方式製得聚碳酸酯,但是使用上述(1)中所製得之183.2 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)呋喃-2,5-二甲酸酯替代實施例1的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。
實施例6
將619 g水、上述實施例1的(1)中所製得之15.4 g雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯(BP-TPDCA)、111.3 g雙酚A、102.5 g 40重量% NaOH、與195 ml MeCl2
放入2 L主反應器中,該主反應器配備氮氣沖刷與冷凝器,且可用環流器保持於室溫,然後攪拌數分鐘。
在停止氮氣沖刷後,將62.81 g三光氣與120 ml MeCl2
放入1 L圓底燒瓶中以溶解其中的三光氣,隨後將所得之經溶解的三光氣溶液慢慢放入主反應器中,其中BP-TPDCA與BPA混合溶液已經溶解。加完後,放入2.5 g PTBP (對三級丁基酚)且攪拌約10分鐘。攪動完後,放入99.4 g 40重量% NaOH水溶液,使得放入1.04 g TEA作為偶合劑。此時,將反應pH保持於11至13。將所得之混合物獨留一段時間以徹底地進行反應,隨後放入HCl以終止反應,使得pH降到3至4。然後,停止攪動,隨後將聚合物層與水層彼此分離,重複地進行三至五次移除水層並再次放入純H2
O的清洗程序。
當清洗徹底完成時,只萃取出聚合物層,隨後經由再沉澱法使用非溶劑(例如甲醇、H2
O等)以獲得聚合物晶體。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計10重量%的由BP-TPDCA衍生之重複單元。
實施例7
以相同於實施例6之方式進行聚合反應,但是使用實施例2的(1)中所製得之15.84 g雙(4-(2-(4-羥基苯基)丙-2-基)苯基)呋喃-2,5-二甲酸酯(BP-FDCA)替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用110.65 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。另外,由NMR分析結果,可確定包括以重複單元總重量為基準計10重量%的由BP-FDCA衍生之重複單元。
實施例8
以相同於實施例6之方式進行聚合反應,但是使用實施例3的(1)中所製得之15.4 g雙(3-羥基苯基)噻吩-2,5-二甲酸酯(BHP-TPDCA)替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用111.3 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計10重量%的由BHP-TPDCA衍生之重複單元。
實施例9
以相同於實施例6之方式進行聚合反應,但是使用實施例4的(1)中所製得之15.4 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯(BPF-TPDCA)替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用111.3 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計10重量%的由BPF-TPDCA衍生之重複單元。
實施例10
以相同於實施例6之方式進行聚合反應,但是使用實施例5的(1)中所製得之15.4 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)呋喃-2,5-二甲酸酯(BPF-FDCA)替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用111.3 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計10重量%的由BPF-FDCA衍生之重複單元。
實施例11
以相同於實施例6之方式進行聚合反應,但是使用實施例4的(1)中所製得之38.5 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用107.2 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計30重量%的由BP-TPDCA衍生之重複單元。
實施例12
以相同於實施例6之方式進行聚合反應,但是使用實施例4的(1)中所合成之62.5 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用101.3 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計50重量%的由BP-TPDCA衍生之重複單元。
實施例13
以相同於實施例6之方式進行聚合反應,但是使用實施例4的(1)中所合成之79.29 g雙(4-(9-(4-羥基苯基)-9H-茀-9-基)苯基)噻吩-2,5-二甲酸酯替代實施例6中的雙(4-(2-(4-羥基苯基)丙-2-基)苯基)噻吩-2,5-二甲酸酯,及使用97.26 g雙酚A。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為50,000 g/mol。由NMR分析結果,可確定包括以重複單元總重量為基準計70重量%的由BP-TPDCA衍生之重複單元。
比較例1
將619 g水、116.5 g雙酚A、102.5 g 40重量% NaOH、與195 ml MeCl2
放入2 L主反應器中,該反應器配備氮氣沖刷與冷凝器,且可用環流器保持於室溫,然後攪拌數分鐘。
在停止氮氣沖刷後,將62.81 g三光氣與120 ml MeCl2
放入1 L圓底燒瓶中以溶解其中的三光氣,隨後將所得之經溶解的三光氣溶液慢慢放入主反應器中,其中BPA已經溶解。加完後,放入2.5 g PTBP (對三級丁基酚)且攪拌約10分鐘。攪動完後,放入99.4 g 40重量% NaOH水溶液,使得放入1.04 g TEA作為偶合劑。此時,將反應pH保持於11至13。將所得之混合物獨留一段時間以徹底地進行反應,隨後放入HCl以終止反應,使得pH降到3至4。然後,停止攪動,隨後將聚合物層與水層彼此分離,重複地進行三至五次之移除水層並再次放入純H2
O的清洗程序。
當清洗徹底完成時,只萃取出聚合物層,隨後經由再沉澱法使用非溶劑(例如甲醇、H2
O等)以獲得聚合物晶體。此時,所製得之聚碳酸酯的重量平均分子量以PS標準物為基準計為49,000 g/mol。
實驗例:聚碳酸酯之物理性質評估
藉助下列方法測量上述實施例與比較例中所製得之聚碳酸酯的射出成型樣本之特性,並且在表1顯示其結果。
*重量平均分子量(Mw):將200 mg聚合物樹脂在200 ml四氫呋喃(THF)溶劑中稀釋以製造約1000 ppm的樣本。然後,用RI偵測器在1 ml/分鐘流率下藉由使用Agilent 1200系列GPC設備測得分子量。關於計算樣本之分子量的標準,藉由測量八個PS標準物描繪出校準曲線,隨後據此計算出樣本分子量。
*流動性(MI):根據ASTM D1238 (300℃,1.2 kg條件)測得。
*折射率(nD):根據JIS-K-7142使用Abbe折射計針對1/8吋厚之樣本測得。(23℃,波長589 nm)
*耐候性指數(ΔE):針對1/8吋厚之樣本測得,根據ASTM D7869,測量樣本之L、a與b值及將該樣本留在風化條件中2250 hr後用Weather-Ometer®機器再度測量L'、a'與b'值。從結果來看,根據下列式1計算出耐候性指數(ΔE)。
[方程式1]
[表1]
關於上表1,使用來自化學式3之單體的包括噻吩結構的單體所製得之聚碳酸酯一般顯示比使用包括呋喃結構的單體所製得之聚碳酸酯更高的折射特性,而以耐候性來說,使用包括呋喃結構的單體所製得之聚碳酸酯更佳。
同時,在包括本揭露的重複單元之所有實施例情況下,和比較例1之一般BPA聚碳酸酯相比,耐候性更佳。特別地,當包括50重量%或更少,且更佳地約10重量%的化學式1之重複單元時,改善耐候性的效果最高。
當考慮到如上述之結果時,在製備用於高折射率目的(例如鏡片)之聚碳酸酯情況下,較佳為包括高含量之具有噻吩結構的化學式3之單體。在製備需要耐候性的聚碳酸酯情況下,有利的做法是包括低含量之具有呋喃結構的化學式3之單體。從而,似乎可藉由依據其目的而適當地調整其含量與單體的方式來製得具有所欲物理性質之聚碳酸酯。The present disclosure will be described in more detail through the following embodiments. However, the following embodiments are provided only to illustrate the present disclosure, so that the present disclosure is not limited thereto. [Example] Preparation Example 1 of Polycarbonate (1) BP-TPDCA (bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)thiophene-2,5-dimethyl acid esters) ![Figure 02_image029](https://patentimages.storage.***apis.com/01/af/27/2c9baffb086fde/02_image029.png)
Dissolve 15 g of thiophene-2,5-dicarboxylic acid in 100 ml of dichloromethane solvent in a round bottom flask, then add 24.3 g of acetyl chloride and 0.29 g of DMF dropwise at room temperature, and stir at room temperature for about 4 Hour. When the resulting reactant became transparent and did not form any foam, the reactant was slowly added to 41.7 g of bisphenol A, 27.6 g of pyridine and 200 ml of dichloromethane solvent without individual purification procedures, and stirred at room temperature for 24 Hour. Add 50 ml of 35% HCl to terminate the reaction, and then wash with water and dichloromethane. The final compound, bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)thiophene-2,5-dicarboxylate (weight average molecular weight: 1,300 g/mol). In this case, compounds in which n is 1 to 4, respectively, are obtained in the form of mixtures. Fig. 1 shows 1 H-NMR (CDCl 3 -d 1 ) of the compound. (2) Preparation of polycarbonate resin Mix 247 g of water, 138.8 g of bis(4-(2-(4-hydroxyphenyl)prop-2-yl)phenyl)thiophene obtained in the above (1)- 2,5-dicarboxylate, 41 g of 40 wt% NaOH, and 165 ml of MeCl were placed in a 2 L main reactor equipped with a nitrogen flush and a condenser, and could be maintained at room temperature with a circulator, Then stir for a few minutes. After stopping the nitrogen flushing, 23 g triphosgene and 60 g MeCl were put into a 1 L round bottom flask to dissolve the triphosgene therein, and then the resulting dissolved triphosgene solution was slowly put into the main reactor, Wherein the BP-TPDCA solution has been dissolved. After the addition, 1 g of PTBP (p-tertiary butylphenol) was added and stirred for about 10 minutes. After stirring, 39.8 g of 40% by weight NaOH aqueous solution were put in, so that 0.42 g of TEA was put in as a coupling agent. At this point, the reaction pH was maintained at 11-13. The resulting mixture was left alone for a period of time to complete the reaction, and then HCl was added to terminate the reaction so that the pH dropped to 3-4. Then, the agitation was stopped, and then the polymer layer and the water layer were separated from each other, and the cleaning procedure of removing the water layer and putting in pure H 2 O was repeated three to five times. When the washing is completely completed, only the polymer layer is extracted, followed by reprecipitation using a non-solvent (such as methanol, H 2 O, etc.) to obtain polymer crystals. At this time, the weight average molecular weight of the obtained polycarbonate was 50,000 g/mol based on the PS standard. Example 2 (1) Preparation of BP-FDCA (bis(4-(2-(4-hydroxyphenyl)prop-2-yl)phenyl)furan-2,5-dicarboxylate) Synthesize in the same manner as in Example 1, but replace the thiophene-2,5-dicarboxylic acid in Example 1 with 15 g of 2,5-furandicarboxylic acid, and use 26.8 g of acetyl chloride, 0.33 g of DMF, 46.1 g bisphenol A, and 30.4 g pyridine. The final compound, bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)furan-2,5-dicarboxylate (weight average molecular weight: 1,250 g/mol). In this case, compounds in which n is 1 to 4, respectively, are obtained in the form of mixtures. Fig. 2 shows 1 H-NMR (acetone-d 6 ) of the compound. (2) Preparation of polycarbonate resin Polycarbonate is obtained in the same manner as the polycarbonate resin of Example 1, but 126.7 g of bis(4-(2- (4-hydroxyphenyl) prop-2-yl) phenyl) furan-2,5-dicarboxylate instead of bis (4-(2-(4-hydroxyphenyl) prop-2-yl) of Example 1 )phenyl)thiophene-2,5-dicarboxylate. At this time, the weight average molecular weight of the obtained polycarbonate was 50,000 g/mol based on the PS standard. Example 3 (1) Preparation of BHP-TPDCA (bis(3-hydroxyphenyl)thiophene-2,5-dicarboxylate) Synthesized in the same manner as in Example 1, but using 15 g of thiophene-2,5-dicarboxylic acid in Example 1, and using 20.1 g of resorcinol and 41.4 g of pyridine instead of 24.3 g of acetyl chloride, 0.29 g DMF, and bisphenol A. The final compound, namely, bis(3-hydroxyphenyl)thiophene-2,5-dicarboxylate (weight average molecular weight: 850 g/mol) was obtained in a final yield of 97%. In this case, compounds in which n is 1 to 4, respectively, are obtained in the form of mixtures. Fig. 3 shows 1 H-NMR (acetone-d 6 ) of the compound. (2) Preparation of polycarbonate resin Polycarbonate was prepared in the same manner as the polycarbonate resin of Example 1, but using 75.4 g of bis(3-hydroxyphenyl) prepared in (1) above )thiophene-2,5-dicarboxylate instead of bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)thiophene-2,5-dicarboxylate of Example 1. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. Example 4 (1) Preparation of BPF-TPDCA (bis(4-(9-(4-hydroxyphenyl)-9H-fluorene-9-yl)phenyl)thiophene-2,5-dicarboxylate) Synthesis was carried out in the same manner as in Example 1, but using 15 g of thiophene-2,5-dicarboxylic acid from Example 1, and using 62.6 g of 4,4'-(9H-fluorene-9,9-diyl)di Phenol and 41.4 g pyridine replaced 24.3 g acetyl chloride, 0.29 g DMF, and bisphenol A. The final compound, bis(4-(9-(4-hydroxyphenyl)-9H-fluorene-9-yl)phenyl)thiophene-2,5-dicarboxylate (weight Average molecular weight: 1,800 g/mol). In this case, compounds in which n is 1 to 4, respectively, are obtained in the form of mixtures. Fig. 4 shows 1 H-NMR (acetone-d 6 ) of the compound. (2) Preparation of polycarbonate resin Polycarbonate was obtained in the same manner as the polycarbonate resin of Example 1, but using 195.9 g of bis(4-(9- (4-hydroxyphenyl)-9H-fluorene-9-yl)phenyl)thiophene-2,5-dicarboxylate substitutes two (4-(2-(4-hydroxyphenyl)propane- 2-yl)phenyl)thiophene-2,5-dicarboxylate. At this time, the weight average molecular weight of the obtained polycarbonate was 50,000 g/mol based on the PS standard. Example 5 (1) Preparation of BPF-FDCA (bis(4-(9-(4-hydroxyphenyl)-9H-fluorene-9-yl)phenyl)furan-2,5-dicarboxylate) Synthesized in the same manner as in Example 1, but using 15 g of 2,5-furandicarboxylic acid instead of thiophene-2,5-dicarboxylic acid in Example 1, and using 69 g of 4,4'-(9H- 9,9-diyl)diphenol and 45.6 g pyridine replaced 26.8 g oxalyl chloride, 0.33 g DMF, and bisphenol A. The final compound, bis(4-(9-(4-hydroxyphenyl)-9H-fluorene-9-yl)phenyl)furan-2,5-dicarboxylate (weight Average molecular weight: 1,760 g/mol). In this case, compounds in which n is 1 to 4, respectively, are obtained in the form of mixtures. Fig. 5 shows 1 H-NMR (acetone-d 6 ) of the compound. (2) Preparation of polycarbonate resin Polycarbonate is obtained in the same manner as the polycarbonate resin of Example 1, but 183.2 g of bis(4-(9- (4-hydroxyphenyl)-9H-fluorene-9-yl)phenyl)furan-2,5-dicarboxylate substitutes the bis(4-(2-(4-hydroxyphenyl)propane- 2-yl)phenyl)thiophene-2,5-dicarboxylate. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. Example 6 With 619 g of water, 15.4 g of bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)thiophene-2 obtained in (1) of the above-mentioned Example 1, 5-dicarboxylate (BP-TPDCA), 111.3 g bisphenol A, 102.5 g 40 wt% NaOH, and 195 ml MeCl were placed in a 2 L main reactor equipped with a nitrogen flush and a condenser, And can be kept at room temperature with a circulator, and then stirred for several minutes. After stopping the nitrogen flushing, 62.81 g of triphosgene and 120 ml of MeCl were put into a 1 L round bottom flask to dissolve the triphosgene therein, and then the resulting dissolved triphosgene solution was slowly put into the main reactor, Wherein the mixed solution of BP-TPDCA and BPA has been dissolved. After the addition was complete, 2.5 g of PTBP (p-tertiary butylphenol) was added and stirred for about 10 minutes. After stirring, 99.4 g of 40% by weight NaOH aqueous solution was put in, so that 1.04 g of TEA was put in as a coupling agent. At this point, the reaction pH was maintained at 11-13. The resulting mixture was left alone for a period of time to complete the reaction, and then HCl was added to terminate the reaction so that the pH dropped to 3-4. Then, the agitation was stopped, and then the polymer layer and the water layer were separated from each other, and the cleaning procedure of removing the water layer and putting in pure H 2 O was repeated three to five times. When the washing is completely completed, only the polymer layer is extracted, followed by reprecipitation using a non-solvent (such as methanol, H 2 O, etc.) to obtain polymer crystals. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 10% by weight of repeating units derived from BP-TPDCA was included based on the total weight of repeating units. Example 7 Polymerization was carried out in the same manner as in Example 6, but using 15.84 g of bis(4-(2-(4-hydroxyphenyl)prop-2-yl) obtained in (1) of Example 2 ) phenyl) furan-2,5-dicarboxylate (BP-FDCA) instead of bis (4-(2-(4-hydroxyphenyl) prop-2-yl) phenyl) thiophene in Example 6- 2,5-dicarboxylate, and 110.65 g of bisphenol A was used. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. In addition, from the results of NMR analysis, it was confirmed that 10% by weight of repeating units derived from BP-FDCA was included based on the total weight of repeating units. Example 8 Polymerization was carried out in the same manner as in Example 6, but using 15.4 g of bis(3-hydroxyphenyl)thiophene-2,5-dicarboxylate ( BHP-TPDCA) instead of bis(4-(2-(4-hydroxyphenyl)prop-2-yl)phenyl)thiophene-2,5-dicarboxylate in Example 6, and using 111.3 g of bisphenol a. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 10% by weight of repeating units derived from BHP-TPDCA was included based on the total weight of repeating units. Example 9 Polymerization was carried out in the same manner as in Example 6, but using 15.4 g of bis(4-(9-(4-hydroxyphenyl)-9H- 9-yl)phenyl)thiophene-2,5-dicarboxylate (BPF-TPDCA) instead of bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) in Example 6 ) thiophene-2,5-dicarboxylate, and 111.3 g of bisphenol A were used. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 10% by weight of repeating units derived from BPF-TPDCA was included based on the total weight of repeating units. Example 10 Polymerization was carried out in the same manner as in Example 6, but using 15.4 g of bis(4-(9-(4-hydroxyphenyl)-9H- 9-yl)phenyl)furan-2,5-dicarboxylate (BPF-FDCA) instead of bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl in Example 6 ) thiophene-2,5-dicarboxylate, and 111.3 g of bisphenol A were used. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 10% by weight of repeating units derived from BPF-FDCA was included based on the total weight of repeating units. Example 11 Polymerization was carried out in the same manner as in Example 6, but using 38.5 g of bis(4-(9-(4-hydroxyphenyl)-9H- 9-yl) phenyl) thiophene-2,5-dicarboxylate substitutes two (4-(2-(4-hydroxyphenyl) prop-2-yl) phenyl) thiophene-2 in embodiment 6, 5-dicarboxylate, and 107.2 g of bisphenol A was used. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 30% by weight of repeating units derived from BP-TPDCA were included based on the total weight of repeating units. Example 12 Polymerization was carried out in the same manner as in Example 6, but using 62.5 g of bis(4-(9-(4-hydroxyphenyl)-9H-terpinene-9) synthesized in (1) of Example 4 -yl)phenyl)thiophene-2,5-dicarboxylate instead of bis(4-(2-(4-hydroxyphenyl)prop-2-yl)phenyl)thiophene-2,5 in Example 6 - dicarboxylate, and 101.3 g of bisphenol A was used. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 50% by weight of the repeating unit derived from BP-TPDCA was included based on the total weight of the repeating unit. Example 13 Polymerization was carried out in the same manner as in Example 6, but using 79.29 g of bis(4-(9-(4-hydroxyphenyl)-9H-terpinene-9) synthesized in (1) of Example 4 -yl)phenyl)thiophene-2,5-dicarboxylate instead of bis(4-(2-(4-hydroxyphenyl)prop-2-yl)phenyl)thiophene-2,5 in Example 6 - dicarboxylate, and use 97.26 g of bisphenol A. At this time, the weight average molecular weight of the obtained polycarbonate was 50,000 g/mol based on the PS standard. From the results of NMR analysis, it was confirmed that 70% by weight of repeating units derived from BP-TPDCA was included based on the total weight of repeating units. Comparative Example 1 Put 619 g of water, 116.5 g of bisphenol A, 102.5 g of 40% by weight NaOH, and 195 ml of MeCl into a 2 L main reactor, which is equipped with nitrogen flushing and a condenser, and can be maintained by a circulator at room temperature, then stirred for several minutes. After stopping the nitrogen flushing, 62.81 g of triphosgene and 120 ml of MeCl were put into a 1 L round bottom flask to dissolve the triphosgene therein, and then the resulting dissolved triphosgene solution was slowly put into the main reactor, Wherein BPA has been dissolved. After the addition was complete, 2.5 g of PTBP (p-tertiary butylphenol) was added and stirred for about 10 minutes. After stirring, 99.4 g of 40% by weight NaOH aqueous solution was put in, so that 1.04 g of TEA was put in as a coupling agent. At this point, the reaction pH was maintained at 11-13. The resulting mixture was left alone for a period of time to complete the reaction, and then HCl was added to terminate the reaction so that the pH dropped to 3-4. Then, the agitation was stopped, and then the polymer layer and the water layer were separated from each other, and the cleaning procedure of removing the water layer and putting pure H 2 O again was repeated three to five times. When the washing is completely completed, only the polymer layer is extracted, followed by reprecipitation using a non-solvent (such as methanol, H 2 O, etc.) to obtain polymer crystals. At this time, the weight average molecular weight of the obtained polycarbonate was 49,000 g/mol based on the PS standard. Experimental Example: Evaluation of Physical Properties of Polycarbonate The properties of the injection-molded samples of polycarbonate produced in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1. * Weight average molecular weight (Mw): 200 mg of polymer resin was diluted in 200 ml of tetrahydrofuran (THF) solvent to make a sample of about 1000 ppm. Then, the molecular weight was measured by using Agilent 1200 series GPC equipment with RI detector at a flow rate of 1 ml/min. Regarding the standard for calculating the molecular weight of the sample, a calibration curve was drawn by measuring eight PS standards, and then the molecular weight of the sample was calculated accordingly. *Fluidity (MI): Measured according to ASTM D1238 (300°C, 1.2 kg condition). *Refractive index (nD): Measured according to JIS-K-7142 using an Abbe refractometer on a 1/8 inch thick sample. (23°C, wavelength 589 nm) *Weather resistance index (ΔE): Measured on a 1/8 inch thick sample, according to ASTM D7869, measure the L, a and b values of the sample and leave the sample in weathering conditions at 2250 After hr, the L', a' and b' values were measured again with a Weather-Ometer® machine. From the results, the weather resistance index (ΔE) was calculated according to the following formula 1. [Formula 1] [Table 1] Regarding the above Table 1, polycarbonates prepared using monomers including a thiophene structure derived from monomers of Chemical Formula 3 generally show higher refractive characteristics than polycarbonates prepared using monomers including a furan structure, while In terms of weather resistance, the polycarbonate prepared by using a monomer including a furan structure is better. At the same time, compared with the general BPA polycarbonate of Comparative Example 1, the weather resistance of all the examples including the repeating unit of the present disclosure is better. In particular, when the repeating unit of Chemical Formula 1 is included in an amount of 50% by weight or less, and more preferably about 10% by weight, the effect of improving weather resistance is the highest. When considering the results as above, in the case of preparing polycarbonate for high refractive index purposes such as lenses, it is preferable to include a high content of the monomer of Chemical Formula 3 having a thiophene structure. In the case of preparing polycarbonate requiring weather resistance, it is advantageous to include a low content of the monomer of chemical formula 3 having a furan structure. Thus, it seems possible to obtain polycarbonate having desired physical properties by appropriately adjusting its content and monomers according to its purpose.